CHEM 202

Distribution of Species in aquatic systems

Textbook: VanLoon & Duffy

CHAPTER 10

Environmental Chemistry
Introduction

The species distribution or SPECIATION for an element or a compound

depends on the nature of the chemical and also on the particular environmental
conditions in which it is found.

It is often possible to calculate or predict the forms that will be present,

assuming one has available the appropriate analytical data and the required
thermodynamic constants.

For rigorous calculations, activities rather than concentrations should be used,

but this requires knowledge of the total ionic composition of the solution.

In many situations, the errors generated by neglecting activity coefficients are

smaller than those arising from uncertainties in the analytical data available for
multicomponent environmental materials.
Introduction

Two calculation situations are encountered:

1. Detailed individual calculations related to specific sets of conditions-for ex, a

calculation how to show what fraction of an acidic species is in protonated
and what fraction is in deprotonated form at a given solution pH.

2. Diagrams that show how species distributions can vary as conditions

change. In the process of constructing such diagrams, methods for
calculation individual situations become clear. There are many kinds of
distribution diagrams.

We will look into the

construction of phosphorus
species diagram and Cd
chloro complexes species
diagram.
Single Variable Diagrams: Phosphate species
A single variable diagram is a plot of some measure of species concentration (y-axis)
versus a particular variable like pH, redox status, or concentration of an important
complexing ligand (x-axis).

A well known case, useful for describing the chemistry of species that exhibit acid-base
behavior, is a plot of a (alpha), the fractional concentration, of individual species against
pH.

A good ex of this application is the phosphate system. Phosphorus exists in water

almost exclusively as P(V) species, particularly in forms of orthophosphate.

To calculate the distribution of these 4 species as a function of pH we need only know

the values of the acid dissociation constants. These three equilibrium constants apply to
successive dissociation from the acid of its three protons, and apply to an aqueous
solution at 25C.
For ex, the first dissociation is approximated by the relation:
Single Variable Diagrams: Phosphate species

The fraction, a H3PO4 of undissociated H3PO4 in a solution containing phosphate species is

Single Variable Diagrams: Phosphate species

Florida eutrophication

From Eq 10.3
Single Variable Diagrams: Phosphate species
Single Variable Diagrams: Phosphate species
Note that each of eqs 10.12-10.15 can be used to calculate the fraction of an individual
species in the phosphate system at a given pH. When the a values are plotted over a
range of pH values, we have a distribution diagram.

Calculating and plotting are most conveniently done using a std spreadsheet-type
computer program.

This Fig. is the plot for phosphate species The village is approximately ½ mile from
the shores of a bountiful yet bacteria and
distribution over the pH from 0 to 14. parasite-polluted water source, Lake
Victoria.
Single Variable Diagrams: Phosphate species
Using this plot, estimates of the phosphorus species distribution are readily made. For
ex, in open water of the Kenyan (eastern) part of Lake Victoria, phosphorus levels are
typically about 12mg/L (as P) and the pH of the water is 8.2.

Under these conditions, the fractional values of the principal species are given by points
where line a intersects the species curves and it is estimated graphically that a H2PO4- =
0.08 and a HPO42- = 0.92, giving concentrations [H2PO4-] = 1 mg/L and [HPO42-] = 11
mg/L.

This Fig. is the plot for

phosphate species
distribution over the pH
from 0 to 14.
Single Variable Diagrams: Phosphate species
In another setting, a sample of pore water from a forest soil in the Canadian shield, total
soluble phosphorus is 62 mg/L and the pH 4.3.

In this situation, (points on line b) the principal species is almost exclusively [H2PO4-] =
62 mg/L.

This Fig. is the plot

for phosphate
species distribution
over the pH from 0
to 14.
10A. The Effect of Ionic Strength on Solubility of Salts
What Do We Mean by “Ionic Strength”?

Ionic strength, μ, is a measure of the total concentration of ions in solution.

The more highly charged an ion, the more it is counted.

where ci is the concentration of the ith species and zi is its charge. The sum extends over
all ions in solution.

NaNO3 is called a 1:1 electrolyte because the cation and the anion both have a charge of 1.
For 1:1 electrolytes, the ionic strength equals the molarity.
For other stoichiometries (such as the 2:1 electrolyte Na2SO4), the ionic strength is
greater than the molarity.
10A. The Effect of Ionic Strength on Solubility of Salts
What Do We Mean by “Ionic Strength”?
Example Calculation of Ionic Strength
Find the ionic strength of (a) 0.10 M NaNO3; (b) 0.010 M Na2SO4; and (c) 0.020 M
KBr plus 0.010 M Na2SO4.
Solution
Note that [Na+] = 0.020 M
because there are two
moles of Na+ per mole of
Na2SO4.
10B. Activity Coefficients
(8-1)

The equilibrium constant expression in Equation 8-1 does not predict any effect of
ionic strength on a chemical reaction.

To account for the effect of ionic strength, concentrations are replaced by activities:

Activity of C
(8-4)

The activity of species C is its concentration multiplied by its activity

coefficient. The activity coefficient measures the deviation of behavior from
ideality.

If the activity coefficient were 1, then the behavior would be ideal and the form
of the equilibrium constant in Equation 8-1 would be correct.

The correct form of the (8-5)

equilibrium constant is
10B. Activity Coefficients
10B-2.1 Activity Coefficients of Ions
Table 8-1 lists sizes (α) and activity coefficients of many ions. All ions of the same size and
charge appear in the same group and have the same activity coefficients.

For example, Ba2+ and succinate ion [–O2CCH2CH2CO2–, listed as (CH2CO2-)2] each have a size
of 500 pm and are listed among the charge = ±2 ions.
At an ionic strength of 0.001 M, both of these ions have an activity coefficient of 0.868.
Single Variable Diagrams: Phosphate species

Effect of ion strength and activity coefficients

Soil solution typically have an ionic strength of 0.002, which leads to an activity
coefficient of about 0.95 for a singly charged ion.

Incorporating the activity coefficient into the calculation would make only a small
difference and the correction would be even smaller for the lake water.

While assuming zero ionic strength in this situation leads to a small error, the error could
be much larger for medium like sea water that contains a high ionic concentration.

Apparent acid dissociation constants have been calculated for phosphoric acid in sea
water:

A substantially different
distribution diagram would
apply to sea water compared
with that calculated above for a
fresh water system.
Single Variable Diagrams: Cadmium Complexes with Chloride

As an ex, we will consider the distribution of aqueous cadmium chloro complexes as a

function of chloride ion concentration.

Again we will use concentrations rather than activities in the calculation.

We start by assuming that, in the absence of chloride or any other complexing ligand,
cadmium exists in aqueous solution as an aquo complex, perhaps Cd(H2O)42+. (Cd2+)

This aquo complex remains without significant deprotonation as long as the pH is less
than about 8.5. Cl- forms complexes with cadmium in a stepwise fashion, with
displacement of one water molecule each time a chloride is added.

We apply the general relations for

complex formation to the cadmium /
chloride situation.
Single Variable Diagrams: Cadmium Complexes with Chloride
We apply the general relations for complex formation to the cadmium / chloride situation.
Single Variable Diagrams: Cadmium Complexes with Chloride

We can derive expressions for the conc of each of the five cadmium species in the
following way. We begin by dividing the above eq by [Cd2+]:
Single Variable Diagrams: Cadmium Complexes with Chloride

We can derive expressions for the conc of each of the five cadmium species in the
following way. We begin by dividing the above eq by [Cd2+]:
Single Variable Diagrams: Cadmium Complexes with Chloride
Again, using an appropriate computer program, the fraction, a, of each cadmium
species can be calculated as a function of [Cl-]. For Cl-, we choose a range of values
from 0 to 0.56 M, the latter being the [Cl-] in sea water.

The plot then forms another type of distribution diagram and is shown below.

This fig. can

be useful in
several
situations.

For ex we
may use it to
describe the
changing Cd
species
distribution
in an
estuary.
Single Variable Diagrams: Cadmium Complexes with Chloride
This fig. can be useful in several situations. For ex we may use it to describe the
changing Cd species distribution in an estuary.

An estuary has been defined as a semi-enclosed coastal body of water which has a
free connection with the open sea and within which seawater is measurably diluted with
fresh water derived from land drainage.

A principal feature of any estuary is a regular variation in dissolved salt conc as one
moves from the inflowing river to the mouth where it opens out into the ocean.

In the vertical dimension, there is a steady but

sometimes irregular increase in salt conc with
depth. There are also marked seasonal fluctuations
in conc, with reduced levels being characteristic of
periods of heavy precipitation or surface runoff.

An estuary is where a river meets the ocean.

Single Variable Diagrams: Cadmium Complexes with Chloride
The Chesapeake Bay in Maryland, USA is at the mouth of the Susquehanna River and
is the largest estuary on the Atlantic coast of the US.

Chesapeake Bay is the largest estuary in the

United States. Partially enclosed by Maryland
and Virginia and almost 200 miles long, the
Chesapeake Bay outlets into the Atlantic Ocean.

Salinity is the mass in grams of the

solid that can be obtained from 1
kg of sea water after all the
carbonate is converted to oxide,
the bromine and iodine replaced by
chlorine, all organic matter
oxidized, and the residue dried at
480C to constant weight.
Single Variable Diagrams: Cadmium Complexes with Chloride
The Chesapeake Bay in Maryland, USA is at the mouth of the Susquehanna River and
is the largest estuary on the Atlantic coast of the US.

The below fig shows the spring–time variation in salinity in a vertical section along the
axis of Chesapeake Bay.

Salinity is the mass

in grams of the solid
that can be obtained
from 1 kg of sea
water after all the
carbonate is
converted to oxide,
the bromine and
iodine replaced by
chlorine, all organic
matter oxidized, and
the residue dried at
480C to constant
weight.
Single Variable Diagrams: Cadmium Complexes with Chloride
The symbol commonly used for salinity is %o which is equivalent to per cent but with the
base of one thousand. Sea water has an average salinity of 35%o (or 3.5%)
representing a chloride conc of ~ 0.56 mol/L.
For the present discussion, we will assume a direct linear relation between salinity and
chloride molarity.

We can now estimate

the fractional
distribution of Cd
species throughout the
estuary.
At the outlet of the
Susquehanna River
(Salinity ~1%0, [Cl-] ~
0.02 mol/L) as
represented by line a,
the approximate
fractions of the three
principal species are
Cd2+ = 0.29, CdCl+ = 0.64, CdCl2 = 0.07
At very low [Cl-] there is considerable tendency for formation of complexes.
Single Variable Diagrams: Cadmium Complexes with Chloride
About half way (144 km) down the Bay the surface water salinity has increased to
10%o, corresponding to [Cl-] = 0.16 mol/L (line b).
At this point, the species have fractions as follows:
Cd2+ = 0.04, CdCl+ = 0.52, CdCl2 = 0.33, CdCl3- = 0.10 and CdCl42- = 0.01.

Near the mouth of Chesapeake Bay, the salinity surface water is 23%o or [Cl-] = 0.37
mol/L. This correspond to line (c). Here the Cd species fractional distribution is
CdCl+ = 0.26, CdCl2 = 0.39, CdCl3- = 0.29 and CdCl42- = 0.06.
Single Variable Diagrams: Cadmium Complexes with Chloride

It should not be surprising that Cd present in estuarine water shows increasing

tendency to be complexed with Cl- as one moves to higher salinity water.

The values we have calculated are fractional results.

Using these along with appropriate measurements of total Cd conc, we could estimate
the amount of each species at any point in the estuary.
Single Variable Diagrams: Cadmium Complexes with Chloride

In the marine environment its toxicity is